Symmetrical di-hydroxyalkylated aminoarsenobenzenes



' Patented Feb. 27, 1940 UNITED STATES 1 2,191,740 SYMMETRICALDI-HYDROXYALKYLATE' "PATENT" el -nee AMINOARSENOBENZENES Alfred Fehrle,Bad Soden in Taunus, and Paul Fritzsche, Frankfort-on-the-Main-Hochst,Germany, assignors to -Winthrop Chemical m- York pany, New York, N. Y.

, a corporation of New I No Drawing. Application December 16', 1937, Se-

rial No. 180,154. In 1936 The present invention relates to symmetricaldi-hydroxyalkylated aminoarsenobenzenes. I

It is known that primary aminobenzene arsonic acids which may stillcontain other substituents in the benzene nucleus form during thereaction symmetrical aminoarsenobenzenes insoluble in water.

Now we have found that symmetrical di-hydroxyalkylatedaminoarsenobenzenes very readily soluble in water are obtained by theintroduction of two equal or different hydroxyalkyl "radicals into theamino group of aminobenzene arsonic acids and a subsequent reduction ofthese acids, for instance by means of hypophosphorous acid or sodiumhydrosulfite. In the same manner the arsonic acids mayfirst betransformed into the corresponding arsine oxides which are then reducedin an acetic acid solution by means of sodium amalgam to obtain the freearsenobenzenes. Furthermore the symmetrical a1senobenzene is directlyformed by the action of an arsine oxide upon the corresponding arsine inan aqueous solution.

By the preceding introduction of the two equal or different hydroxyalkylradicals into the primary arsonic acids performed in known manner by thereaction with alkylene oxides the position of the various hydroxyalkylradicals in the dihydroxyalkylated aminoarsenobenzenes obtained by thereduction of the acids is also exactly defined.

' The compounds thus obtainable correspond to the following generalformula:

ASZAS I R I R X- N X -N a l R I R on on v wherein R stands for ahydroxyalkyl radical and X stands for hydrogen or for the group Allthese compounds form .yellow powders which are insoluble in ethylalcohol and ether and readily soluble in water. They are distinguishedby a high non-toxidity and show, contrary to the monohydroxyalkylated ornon-hydroxyalkylat ed aminoarsenobenzenes, only a very small irritatingeffect when subcutaneously injected.

.The following examples serve to illustrate the invention, but they arenot intended to limit it thereto:

(1) 73.5 grams of the di-hydrochloride of 33'- Germany December- 19, I

2 Claims. (01. 260-445) a a di (bis-dihydroxypropyl) amino-4,4 dihydroxyarsenobenzene are dissolved in 500 cc. of water, the strongly acidsolution is rendered neutral to litmus paper by the addition of sodiumcarbonate and the clear yellow liquid is poured into ethyl alcohol. I pv 3,3fl-di (bisdihydroxypropyl) amino 4A ,dihydroxyarsenobenzene of theformula onaonon'oneon N CH2. 01501 1011103 -N 0112.0HOH1CH2OH cipitatewhich is filtered with suction, washed with ether and, if necessary,purified by again dissolving it in water and precipitating it in ethylalcohol. ;The compound isreadily soluble in water while showing aneutral reaction and is insoluble in ethyl alcohol and ether.

is obtained thereby in the form of a yellow pre-' The same compound isobtained by dissolving j 38.1 grams of 3-(bis-dihydroxypropyl)-amino-4-hydroxybenzene-l-arsonic acid in 38 cc. of water and heating thesolution together with 120 grams of sodium hydrosulfite for about halfan hour a slightly yellow precipitate of 3,3'-bis-(dihydroxypropyl-hydroxyethyl) amino-4=,4'dihydroxyarsenobenzene of theformula ASflAS omfomon -N 1 0H,.0H0110H20H I OH OH CHz.CHzOH NCH2.CHOH.CH2OH separates from this solution and is filtered with vsuction, washed with ether and dried. The preparation is insoluble inethyl alcohol. and ether and readily soluble in water.

CH2.CHOH.CH2OH CHQ.CHOH.CH2OH l N CHSCO.NH N

1 l oHfloo-Nlli cmonouomon cmcnoaomon OH OH separates therefrom which isfiltered with suction, washed with ether and, in order to completelypurify it, is again dissolved in water and precipitated with the aid ofethyl alcoholand ether. The compound is likewise very readily soluble inwater but insoluble in ethyl alcoholand ether.

The same compound is obtained by first transforming 3-(bis-dihmdroxypropyl) -am.ino- 4 -hydroxybenzene-5-acetylamino-l-arsonicacid with the aid of sulfurous acid and potassium iodide into 3-(bis-dihydroxypropyl) -amino-4-hydroxybenzene-S-acetylamino-l-arsineoxide as described in Example 1 of German Patent No. 638,265, datedApril 3, 1935, in the name of I. G. Farbenindustrie Aktiengesellschaft,and 19.5 grams of this arsine oxide in an acetic acid solution arecaused to react in portions with 85 grams of sodium amalgam of 4 percent. strength.

- As soon as all the sodium amalgam has been consumecl, the solution isdecanted from mercury, the clear liquid is stirred into ten timesitsquantity of methyl alcohol, filtered ofi from the inorganic saltsseparated and the yellow filtrate is precipitated in ether. The3,3'-di-(bis-dihydroxypropyl) amino 4,4 dihydroxy 5,5- di- (acetylamino)-arsenobenzene separates thereby in the form of a yellow precipitatewhich is filtered with suction and washed with ether. If furthermore19.5 grams of the above named arsine oxide and 18.8 grams of thecorresponding arsine, which is obtained in the usual manner by i thereduction of arsonic acid by means of zinc dust and hydrochloric acid,are dissolved in cc. of water, the liquid assumes, while heated, a darkyellow color and, while stirring into a mixture of ethyl alcohol andether, a yellow precipitate of 3,3'-di-(bis-dihydroxypropyl) -amino- 4,4dihydroxy 5,5'- di (acetylamino) -arsenobenzene is separated.

We claim:

1. The compounds of the following general formula:

said compound being a yellow powder which is readily soluble in waterand insoluble in ethyl alcohol and ether.

ALFRED FEHIRLE. PAUL FRITZSCHE.

cmcnoaomou CERTIFICATE OF CORRECTION. Patent No., 2,191,7L 0. I February27, 19t

ALFRED FEHRLE, ET AL.

It is hereby certified that the name of the assignee in the abovenumbered patent was erroneously described and specified as "WinthropChemical Company Whereas said name should have been described andspecified as "Winthrop Chemical Company, Inc." as shown by the record ofassignments in this office; and that the said Letters Patent should beread with this correctionv therein that the same may conform to therecord of the case in the Patent Office.

Signed and sealed this 20th day .of June, A. D. 19%.

Leslie Frazer (Seal) Acting Commissioner of Patents.

